Corrosion inhibiting composition



Patented Mar. 23, 1954 JC'UNITED sTArEs PATEN T oFFICEA CORROSION INEDBITING COMPOSITION Edgar Pi. Dienian, Crown Point, Ind., assignor to Standard Gil llompany, Chicago, 111., a corporation of Indiana No Drawing. Application November 27, 1951, Serial No. 258,501

Metal surfaces whenever possible are protected from corrosion and/or rusting by a coating of some kind. In general, two types of protective coatings have been employed, namely permanent and temporary coatings. In the first class are included oxide coatings, phosphate coatings, paints, varnishes and other non-metallic materlals which form dry, hard films. In the second classofprotective coatings which are of the type which, must at some time be readily removed from the surfaces they are protecting are those products prepared from oleaginous materials, such as petroleum oils, petrolatums, waxes, greases, asphalts, etc. While such products give satisfactory protection under certain conditions, under many conditions they do not provide the protection desired, and require the addition thereto ofrust and/or corrosion inhibitors. Anti-rust or-slushing compositions are used for the protection of metals either in the form of stock or fabricated articles against corrosion and/or rusting. Materials prior to storage should be coated with an anti-rust material to prevent corrosion and/or rusting while in storage; and finished or semidinished metal stocks destined for shipment by rall'or by water must be protected against attack by moisture by coating such materials with suitable anti-rust or slushing compounds. Materials for shipment overseas must be protected against attack. by salt spray.

It is an object of the present invention to provide anti-rust compositions which will effectively prevent and/or inhibit corrosion of metal surfaces. Another object of the present invention is to provide improved slushing and/or anti-rust compositions. v

In accordance with the present invention, the foregoing objects can be attained by employing as theLslushing composition an oleaginous material containing in combination from about 0.5% to about of an alkali metal soap of a preferentially oil-soluble sulfonic acid, and from about 0.5% to about of the polymeric residue that is produced in'hydrooarbon synthesis from hydrogen and carbon monoxide in the presence of an iron catalyst, or the alkali metal and/or alka- 2 line earth metal soaps thereof, such as the sodium, lithium, calcium, barium, strontium soaps or mixtures thereof.

The hydrocarbon synthesis, from which the polymeric residue of the present invention are obtained, is usually performed at temperatures from about 390 F. to about 660 F., and under superatmospheric pressures from slightly in excess of atmospheric to as high as 600 pounds per square inch gauge. An increased yield of the polymeric residue is produced when the aforementioned iron catalyst contains an alkali metal oxide or carbonate promoter.

The aforesaid polymeric residue is produced as a primary condensate from the condensible gases that are manufactured in the described hydro carbon synthesis process or it can be a residue from a fractional distillation of liquid product therefrom or it can constitute a mixture of the -v two. These polymeric residues have a pour point.

of substantially room temperature and comprise a mixture of about 85-90% by weight of heavy hydrocarbons and oxygenated compounds, a high proportion of which isunsaturated. Of the hydrocarbons some 20 to 30'percent are paraflinic, and the remaining to percent are olefinic. A very considerable portion of the olefins are mono-olefins. The polymeric residue is soluble in 50-50 benzol-acetone, and ranges in carbon number from about 011 to C35, and perhaps, to

a minor extent, somewhat higher. The product 'contains about 10 to 15 per cent oxygenatedcompounds, including alcohols, aldehydes, acids, esters and ketones.

are normal parafiins, the branching of the chains being largely methyl groups and increasing in number of branched chains per moleculewith increase in molecular weight. At least about 25%,

by weight, of the polymeric residue consists of said oxygenated compounds and hydrocarbons that melt between about l20F.-2l2 F.

Illustrative of a method of obtaining the polyweight balance in synthesis Was recovered from;

the product gases. A portion of the product was Normally, about 5 percent and a maximum of 10 percent of the hydrocarbons recovered by initial condensation at high temperature and the remainder obtained as a residue from the distillation of the liquid hydrocarbons. By mixing the products so obtained in the proportions of their initial formation, a polymeric residue product having a meltin point slightly above room temperature, is obtained". l

A typio'al "l-ymbric residue had the following distillation characteristic and neutralization values:

Percent Collected F.

I sea-590i: Over 590..

em netia with thea ka i meta me or the lly; o' ble petroleum sulfonicer- I; p r: toiiuse the: alkali metali fiidityi ofrthe polymeric-residue;at a temperature-.-.

of from about 200 F; toabout325 R, andthe sol-vent =;;-suctri,as-; .a1 low boiling hydrocarbon, for. example, heXanepnaphtha, etc..

The polymeric residue can be used. as suchin;

is earth, .iet lro ps f hpolyrz tralizedlwithazsolutioni of. sodiumzhydroxidec Irhe: aqueous alkali: solution isa'then. separatedi.i rcurr dllhearpreparfation 'iofuthe calcium; soap of: the;

polymeric residue;v is illustrated bythe. following.

example:: ,i

178023001 giramsi ofi polymeric residue, was added abeim;lG0igram&-of;"Z-5,% ethyl,alcohol-water-solu-- tiqnrboiaot amsolvent during the process of neutrali'zationrx L;- grains (which is about 16% in exoesseof the 'ca-lculatedv amount necessary) ofi.

calcium: hydroxidemvasnmade into a slurry with;

wateniandz-slowlyvadded to the polymeric residuea alcohohand: waited-solution while it; was stirred. witri'lac'mechanical mixer at1150? tempeuatureio whibhapointitheilast of the water was evaporated: anflg;gflqe ;profiugt;f111E619 substantially dry,- The oductswas them cooled to room temperature" andi'dissolvedaimabout 2 "volumes" of hexane.

After allra. thECCZl.-'I(OH)2L='S111=HW had bESIlBfi/dd8d, mixin andiiheating-rwasa'continued at ter'uperaturessufdci'entr. toibnihofi, theaalcoholiandsfinahysthewater: The

theimix Wasraised to-23Q' atz i golumr-portiona and 'unreacted calcium hydrox ideidv'wases'ep'arated-i by: centrifuging from which: 6.5 Wab=- recovered as insoluble material. v The heiranersolubletmaterial was decanted c'if: and:

the hexane evaporated: This-- portion amountedy to 89.5% of th samplemaliing atotalrecovery tiom inclu'cl'e scans of 'alkyl sulfonic acids; petroleumz-sulronic:acids, allraryl sulionic acids-- aniiiaamlkyli sulfonicacids, although I prefer-to useatfieaikali metal soaps of the so-called mahog aminacidsiobtainediin the treatment 01' hydro:- calfibfiii lliflilsyz I about Q5 q s gength; iusually fuming sulfuric. acid.

Thesm-anahpganygacidsi have molecular. weightedto-aboutxdOO. The method-oh s'oap of'the preferentially oil- "'hlistrongz.sulfuric acid of at least:

p tal soaps-gof; the so-called-q Q- er: dumps.

mahogany acids, well known to those acquainted with the petroleum refinin art, i illustrated by the following example, which describes the preparation of the sodium soap.

A petroleum oil distillate having a Saybolt Universal viscosity at F. of from about 200 secon'dszto about :850 second's" is"treat'ed with from about 7 to about tpounds-of 'furhina'sulfuric acid per gallon of oil in one-half pound increments After the acid Sludge from each one-half.poundracidfdump is settled and withdrawn, the next one-half pound of fuming sul- "furic ,a'cidii's .addedztohthe oil. The temperature *o fztheoil-before the-fuming acid is added thereto is maintained-below about 60 F., but due to the heater the reaction upon the addition of the suliur-i'c acid, the temperature of the oil may rise to from about 90 F. to about 109 F. After th'erequir'e'd total amount of fuming sulfuric acid has been added to the oil and the oil freed of aci'da slud'ge i the? acidt-treatedroi l fcohtainingt'oilscluble: sulfonicr acidsndissolved tnerei-n,..is 118115 the 011:. solution containing. dissolvedr: therein sodium soap: or sulfonic: acids and the: latter is: then. separated: from-1 the-oil by extraction; with alcohol ofzaboutr6.tiz% strengthr Thealcoholllayer containing dissolved sodium sulforrates'z..isi.theni separ atedafrom: the-Oil? and; subsequently; distilled to recover: the alcoholiand remover wate rt' IF-h e crude sulfonic soapnobta'ined ih this maniren con-= tains from about: 30%. to about-60% sod; sui fonate; from about 30% to; about 60 "o about 1 to about 10%-- watemand to inorganic salts which: may) be r'r'emove'd by tha proce'dure hereinafter described.-

The above procedurebe modifiediinrthatafter the acid: sludge is:.:removedfrom: the: a treated oil, the: 611 containing: diss'o'lved sulfo acids isextracted with about; 60% alcoholi toiremove the sulfonicacids which m'ay th'en be neu tralizedwithsodium hydroxide anfi subsc'qu'entli freed of the alcohol bydi'stillation v v The crude; soaps of these preferentially "oil soluble suifon-ic-acids obtained -by'th'e procedure described above may be :freed of inorganic: seats by purification. This purification: is referably accomplished dilution of the: crude: soap-"wi from about toabout lo'parts preferably 1 parts 'of 50%; or higher strength alcohol; preferably' alcoholor ob -tote strength; and-chewing the salts=to settle whilemairitaini gthe H170;

ture within the-temperature range of 1B0 1'75 FL, preferably 1 65 1 Wfienthe salts have settld 'the layer is 'se1ir2'u ett'ed and tit-ii alcohol by conventional distillation probed method of purification, the' salt 'content-of tiie crude. sulfo'nic "soap can be readilyreduced to 5% or: less; es g. wetsuits-35%: "Ib facili-tate" handling; the sulfona-te's' are preferably-"dissolved a in a petroleum= oilte -give -a= blend--cofrtai niig* about 35-50% sul'fonat'ea Although in the above exampl anbil o i seconds to-= 850 seconds saybclr- U1 verse cosity at 1- 00 Fiwl ias{been used} itis he having =saybo1t-Universar viscosities at -rot ranging from about -wseconds to about1ot0 sec onds; .onrhigher. Eurthermore; thebulfiir-ic acid employed; canrreihge: from "about 3rtoi about 9 pounds; nen'gallon 10f roilzi V er natant;-alei-incl scap I recovered The; ,vebicleifon-the hereinedescribediinhibitorsa ae'z'arer can" be any of the materials .usually used as the base'for such compositions. These are usually naturalor synthetic hydrocarbon oils covering wide range of viscosities, such as-pctroleum distillates'of relatively low viscosity to distillates or residuums of high viscosities. Solid and semisolid petroleum products such as Waxes and petrolatums' can also be employed. Also waxes and oils of animal, vegetable or marine origin, or mixtures of these with hydrocarbon oils and waxes can be used as the base material. To facilitate application, the composition may be thinnedxwith a volatile solvent, such as a low boiling hydrocarbon naphtha, etc.

The efiectiveness of the herein described composition in inhibiting corrosion is demonstrated byJthe-data in the following table. These data were obtained by subjecting steel test panels coated with the various compositions to the humidity cabinet test and the time before rusting occurs noted in each instance.

xInthe humidity test the steel panels are suspended in a special cabinet described in the National Military Establishment specification designated JAN-H-792(6-21-49), and the time of initial corrosionof the panels noted. The humidity cabinet. is provided with heating units and thermal regulators for automatic temperature control. A water. level is maintained in the bottom" of the cabinet to give approximately 100% humidity at all times. The steel panels are coated by dippinginto the rust preventive material and are suspended in the cabinet by stainless steel or Monel. hooks. The JAN-I-I IBZ specification is modified to the extent that a temperature of 100 F. (L -2 F.) instead of 120 F. (-1: 2 F.) is maintained in the cabinet, and from 1 to 1.5 complete changes of saturated air per hour are provided in the cabinet, instead of 8 :1) linear feet per hour.

Hours in Humidity Cabinet Before Rusting Occurred Run No. Blend 94% Parafl'lnic 011 6% Calcium Soap of Polymeric Resi- 8.

III

due. 92% Paraflim'c Cil f i .l i IV l 6 Soap o o ymenc esi- 350.

2% Sodium Mahogany Soap 92% Paraflimc O1l 6% Polymeric Residue (Unneutral- V u s iggd M h s J l 2 0 mm a ogany oap Controlnbif Less Dthan 8. 257 Paraillnic 75;: g am on.-.

98 o. 295 Sodium Ma P 94% No. VI VIII I. 6% Callcium Soap of Polymeric Resp Less than 8.

92% No. VI 2% Sodium Mahogany Soap 6% Calcium Soap of Polymeric Residue. 94 a No. VI 6 a Baarium Soap of Polymeric Resiue. 92% No. VI XI 2% Sodium Mahogany Soap Less than 8.

6% Barium Soap of Polymeric Residue.

The synergistic eifect of the combination of the sodium mahogany soap and the alkaline earth soapsof the polymeric residue is demonstrated by comparison of runs I and III with runs IV and VI, VII, VIII and X, with runs IX and XI. Run V illustrates the efiectiveness of the combina- 6': tion of mahogany'soap and the unneutralized polymeric residue. T

Similar results are obtainable with other. alka-- line earth aand alkali metal soap of the polymeric residue and other alkali metal sulfonates'. In general, however, the alkali metal-soaps of the polymeric residue are somewhat less efifective than the alkaline earth soaps of such residues.

Polymeric residue from the same source of the polymeric residue used in the above experiments was distilled to obtain a 60% overhead fraction and a 40% bottoms. A portion of the latter was neutralized to obtain the calcium soap thereof,- and the following blends tested for their rust. inhibiting properties.

Hours in Hu- Run N o. Blend midity Cabinet Before Rustlng XII Paraffin Oil.. Less than 8. 04% No. XII XIII 6% Calcium Soap of 40% Bottoms of 8.

Polymeric Residue. i? 5% XII "Erie's 0 a mum Soap o o ottoms of XIV Polymeric Residue.

2% Sodium Mahogany Soap I 04% No. XII XV 6% Unneutralized 40% Bottoms of 8,

Polymeric Residue. i 2? l d fi tt 0 nneu ra ize 40 0 o oms oi XVI Polymeric Residue.

2% Sodium Mahogany Soap YVH 98% No. XII 72 2% Sodium Mahogany Soap The mahogany soaps used in the above tables were blends of 50% soap and 50% petroleum' oil. Y While the herein-described invention finds its primary use in the protection of metal surfaces of metal articles in storage, stand-by equipment,

etc. is also applicable to the protection of metal surfaces of equipment while in service, such as engines, machinery, etc. For such services it may be desired to incorporate in such compositions other additives, such as for example, polymeric thickeners, V. I. improvers, oiliness agents,

pourpoint depressors, antioxidants, etc.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

Although the present invention has been described by reference to specific embodiments thereof, these are given by way of illustration only and the invention is not to be limited thereto, but includes within its scope such modifications and variations as come within the spirit of the appended claims.

I claim:

1. A composition comprising a major propor-. tion of an oleaginous material, from about 0.5% to about 10% of an alkali metal soap of a preferentially oil-soluble sulfonic acid and from about 0.5% to about 25% of a soap selected from the group consisting of an alkali metal soap, an-alkaline earth metal soap and mixtures thereof,- of the acidic constituents of a polymeric residue directly obtained as a product of the synthesis of liquid hydrocarbons from carbon monoxide and hydrogen at a temperature between about 390 F. and 660 F. at superatmospheric pressure in the presence of an alkalized iron catalyst, said polymeric residue consisting predominantly of saturated and olefinic hydrocarbons, and oxygenated organic compounds having between about 11 to about 35 carbon atoms per molecule, and contains at least 25%, by weight, of a mixcompounds m ng between about. 50 3 10.0??011... w

:eemposition as: described in claim 1 in,

whiemthe: preferentially OfirSOlllblE sulionic acid:

bomoflewithz. strong z-suliuric; acid; i

i 31" composition: as described in; claim i: in whichixthex alkali metal soap. of a preferentially;

- oiis-solublensulfomc acid is the sodium soap.

:-1.45'$ Azecnmpositiom as. described; in. claim 1, in;

whichathezalkali; metal soap oi? a preferentially:

which the alkaline earthmetal soap of the polymeric residue is the barium soap;

8. A composition. described in claim 1 in which thev oleaginous material is a normally: liquid hydrocarbon.

9. A composition as described in claim 1 in,

which the oleaginous material is a petroleum oil.

10. A flushing-composition. comprising a majorproportion of a normally liquid hydrocarbon; from about L5% to about 10% of; an alkali metal soap of a preferentially oilesoluble petroleum sulfonic acidand-i-rom about 0.5% to about 25%-0f amaikalineearth: metal soap'oi the acidic cone stitiientsmof ai p olymeric. residue comprising-a} m'i'iitur'e be about 8 to 90%, by Weight dmcarbonsg. said: hydrocarbons being: about? "10% l70 80?.%,' by weight? olefinic; aHdfTDHIJEbOIIH 10% to: about by. weight; oxygenated-organic: compounds liaving between; about; 11 13'0r35'i car.

.- 5*! boni atomsepenmoliaouler at 'least'.25%iby :weighti ism pmeferentiallwoilesoiuble petroleum suliionic;v

acid! obtained-51mm the-treatment of? aahydrocan of the mixture of hydrocarbons zand'zioxygenatedz; organic'compounds'imelting betweemabout 1202mm to: about 212 E3; said; polymeric: residuelbeing; directly obtainedcasna'i productv of. the: synthesis:

I 10 oft liquids hydrocarbons of." carbon monoxideland'i.

hydrogen; in-ixthe presence of. an; alkalizedeiiron. catalystacat a1. temperature between about; 390! and-i 6609- F2, andtatisuperatmospheric. vpressiii'ei.

11. A slushing:= composition comprisinga majon 1 15 proportion-1ofzahydrocarbbn.oi1;:.fromi about 115% toabout 103%; oiian. alkali: metalsoap of; aipz'eita erentially. :oi1-soli1ble PBtIlOIBflIIhSlIlf'DIliC-E acidrandz'a from about 05%; to; about '25 7 of) alkaline:

earth metali soap otathe: acidic constituentsiofi'aa;

ao polymeric residue thatizconsistsa-ptedominantlwz of saturated andzolefinimhydrocarbons androxya, genated-I organic. compounds having, between droearbona: and: oxygenated:organicaiccmpounda1 havinga melting: point. between abouta'lflflb E3 and: 21a? FL, 'saidi polymeric: residue beingmohs v directly arxprocluctzz ofkthe syntheeisrofi: liquid hS fiTDQEJTbUIXSXTfIOmi-Z carbommonoxide: ands hydrogenat a temperature;betweemaboutfiiifl c and; 660" atssuperatmosphericz pnessureaimthet; presencexiofitanzalkalizediiron; catalyst. i

EDGAR; A. .m- A p No references, i 

1. A COMPOSITION COMPRISING A MAJOR PROPORTION OF AN OLEAGINOUS MATERIAL, FROM ABOUT 0.5% TO ABOUT 10% OF AN ALKALI METAL SOAP OF A PREFERENTIALLY OIL-SOLUBLE SULFONIC ACID AND FROM ABOUT 0.5% TO ABOUT 25% OF SOAP SELECTED FROM THE GROUP CONSISTING OF AN ALKALI METAL SOAP, AN ALKALINE EARTH METAL SOAP AND MIXTURES THEREOF, OF THE ACIDIC CONSTITUENTS OF A POLYMERIC RESIDUE DIRECTLY OBTAINED AS A PRODUCT OF THE SYNTHESIS OF LIQUID HYDROCARBONS FROM CARBON MONOXIDE AND HYDROGEN AT A TEMPERATURE BETWEEN ABOUT 390* F. AND 660* F. AT SUPERATMOSPHERIC PRESSURE IN THE PRESENCE OF AN ALKALIZED IRON CATALYST, SAID POLYMERIC RESIDUE CONSISTING PREDOMINANTLY OF SATURATED AND OLEFINIC HYDROCARBONS, AND OXYGENATED ORGANIC COMPOUNDS HAVING BETWEEN ABOUT 11 TO ABOUT 35 CARBON ATOMS PER MOLECULE, AND CONTAINS AT LEAST 25%, BY WEIGHT, OF A MIXTURE OF HYDROCARBONS AND OXYGENATED ORGANIC COMPOUNDS MELTING BETWEEN ABOUT 50* C. AND 100* C. 